Lubricant



Patented Sept. i5, 1951 LUBRICANT David E. Adelson, Berkeley, Calii'., assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application December 22, 1947, Serial No. 793,329

12 Claims. (01. 252-48.

This invention relates to novel reaction products having properties of greatly improving and stabilizing lubricants. This invention also pertains to lubricants, such as mineral lubricating oils, synthetic lubricants of hydrocarbon or nonhydrocarbon origin, and the like, containing therein a multi-functional additive having detergent and anti-ringsticking properties, as well as acting as an inhibitor of oxidation and corrosion.

It is well known that various lubricants whether doped or undoped, tend to oxidize and to form corrosive bodies and sludge, when used in modern engines and machines operating under ordinary conditions or at high speeds, elevated tempera tures, heavy loads and/or other adverse conditions. Some of the deterioration products of lubricants formed during their use are hard carbonaceous materials which adhere to metal surfaces and cause scratching and scuiilng of movable metal parts and the sticking of valves and piston rings in engines. In addition, presently known lubricants are generally incapable of maintaining a continuous lubricating film between movable metal parts, resulting in gradual or rapid wearing away of metal parts. The damage thus caused required replacement of such parts or even the complete overhauling of engines and machines, resulting in expensive loss of production and time.

' In the case of the highest quality non-corrosive, stable lubricating oils, which have been highly refined for specific uses, or synthetic lubricants de-. veloped for specific or special uses, it has been observed that such oils or lubricants are generally highly susceptible to oxidation and deterioration, becoming progressively more corrosive in engines and machines even under ordinary operating conditions.

To improve the lubricating properties of oils and synthetic lubricants it has become the practice to blend with various lubricants, one and in most cases more than one addition agent, which additives have the effect or property of inhibiting deterioration of lubricants and impart to them certain beneficial properties. Thus, additives have been specifically designed which have the property of inhibiting corrosion of alloyed bearings such as copper-lead, cadmium-silver and the like, developed for automotive, diesel and aircraft engines. Acidic oxidation or decomposition components formed in lubricants duringuse readily attack these bearings but are inhibited or prevented from doing this by the formation of a corrosion protective film formed on the bearing surface with the aid of the additive. Additives have also been developed which possess the property of modifying the carbonaceous materials formed, by deterioration of lubricants, on piston rods, rings and valves, and other metal parts in internal combustion engines, automotive and truck engines, aviation engines, high speed diesel engines and the like. Such additives serve a very important function because, by modifying this carbonaceous material so that it can be removed easily, the tendency of engine parts to become stuck is inhibited so that ringsticking, pistonscufllng, scratching and wearing away of other engine parts and material reduction of engine efliciency, are prevented or materially inhibited.

other additives have been developed for the purpose of actingas detergent in lubricants in order to assist in the removal of soot or sludge, varnish, lacquer formed from deterioration of the oil when subjected to high operating temperatures. Detergents due to their cleaning action prevent the build up of these deleterious materials and assist in removing those formed. Antiwear additives have the property of reducing friction of movable metal parts of the same or different metals. Due to the function exerted or property imparted by such additives on lubricants, wear caused by direct frictional contact of metals can be greatly reduced. Also, additives have been developed to withstand extreme pressures, disperse impurities, solubilize certain additives and the like.

The development of numerous additives has been due to the fact that most, if not all additives are capable of functioning in substantially only one specific manner. Very few lubricant additives have the ability of improving a lubricant in more than just one respect. Thus. a good antioxidant might not be able to inhibit lacquer and varnish formation on piston rods or act as a detergent or corrosion inhibitor. In many cases it is found that an additive possesses very good properties in one respect, but is the cause of harmful formations and therefore detrimental as an additive in another respect. Therefore, other additives are frequently required to obtain a good stable lubricant. The combination of additives in lubricants wherein each additive exerts its influence without interfering with the function of other additives is a difficult matter to attain. In mostcases additives co-react or interfere with each other. To prevent this great care must be taken in selecting the additives, mixing them in specific proportions and continuously watching and replacing additives which have stopped functioning or have deteriorated.

It is an object of this invention to improve the lubricating properties of various lubricating bases by the addition thereto of a minor amount of a multi-functional material. Another object of this vinvention is to add to compounded or doped lubricants a multi-functional material whereby a synergistic efiect is produced, resulting in a product of accentuated and improved properties. Another object of this invention is to add to oleaginous materials, mineral lubricating oils, synthetic lubricants and the like, a multi-functional material so as to inhibit oxidation and corrosion and prevent the formation of sludge, varnish and lacquer in said lubricants even under adverse operating conditions. Still another object of this invention is to use in lubricating compositions, a multi-functional material which prevents ringsticking as well as the sticking of other engine parts due to deterioration of the lubricant. Also it is an object of this invention to use in oleaginous materials, e. g. in lubricating composions, a multi-functional material which inhibits wear, scuffing, scratching and other damage to engine parts. Furthermore it is an object of this invention to provide novel multifunctional improving and enhancing additives for lubricating bases. Other objects of this invention will appear as the description proceeds. To the accomplishment of the foregoing and related ends, thisinvention consists of features which will be hereinafter fully described, and particularly pointed out in the claims, the following description setting forth in detail certain embodiments of the invention, these being illustrative of but a few variations in which the principle of the invention may be employed.

Broadly stated. this invention is directed to the use, in lubricants of peroxide catalyzed reaction products of organic compounds having an unsaturated linkage or linkages between two or more atoms, with, reactive polyhalogenated organic compounds. Another embodiment of this invention is to form a peroxide catalyzed reaction product of organic compounds having an unsaturated linkage or linkages between two or more atoms, with reactive polyhalogenated organic compounds, and thereafter treating-said reaction products with hydrogen sulfide in the presence of ammonium hydrosulfide. The above reaction products may be used as such or neutralized with metals or organic bases to form salts thereof and added in minor amounts to a desired lubricant. Among the organic compounds which can be used to form reaction products of this invention are:

I. Unsaturated hydrocarbon compounds:

Z-methyl-l-pentene 4-methyl-2-pentene l-decene l-dodecene l-cetene l-octadecene Olefinic hydrocarbons, e. g. wax olefins; Olefin obtained by decarbonylation of oleyl alcohol or such unsaturated alcohols as are obtained by carboxyl reduction of sperm alcohol; Oleflns obtained by dehydration of high molecular weight saturated alcohols, etc. B. Acetylenes- Butine Crotonylene Pentine Valerylene Hexine Hexoylene Heptine Phenyl acetylene Oenanthylldiene Octine Caprylidene Decine Menthene Dodecylidine and their homologues and analogues. C. Cyclic type hydrocarbons Cyclopentane Cyclopentadiene Cyclohexene l-ethylcyclopentene-l 1,2dimethylcyclopentene-l 1-methyl-2-ethylcyclohexene-1 1,3-dimethylcyclohexadiene-1,3 1-cyclopentylcyclopentene-1 Cyclo-octene Cyclobutene Cyclobutylene Cyclohexadiene Cyclopropane Cycloheptadecene Cycloheptatriene Cyclo-octadiene, etc. D. Cyclic terpenes Cymene Penchene Limonene Linonene Pinene Sabinene Bornylene Thujene Methene Terpinene Terpin Cadinene Terpinolene Clovene Camphene Diterpenes Carene v Polyterpenes, etc. E. Aromatic type hydrocarbons- Benzene Naphthalene Anthracene Phenanthracene Biphenyl Diphenylalkenes Stibene Diphenylalkanes, e. g.

Dlphenyl methane Alpha-methyl styrene Phenylacetylene Phenyl propyne-l, etc.

Compounds under group I, A to E, may contain substituent groups such as alkyl, hydroxy, amine, nitro, nitroso, halogen, carboxyl, mercapto, cyano, etc.

II-A. Polymeric and co-polymeric compounds (Q obtained by polymerizing compounds under group I-A to E and mixtures thereof. Specific preferred polymeric compounds are:

Ethylene polymers Isobutylene polymers Butene polymers Butadiene polymers Polymeric material obtained from cracked gasoline fractions Polymeric materials obiained from cracked paraffin waxes Polymeric materials obtained from recycle stock from petroleum cracking operation Polymers obtained by dehalogenating wax olefines Polymers obtained by destructive hydrogenation of rubber olefin polymers obtained from dehalogenating long chain alkyl halides, etc.

B. Polymers obtained from alkene halides, e. g.

Vinyl halides 2-halo-propylene Crotylhalides Allylhalides 2-methyl-3-chlorpropene Methallyl chloride Z-ethyl-B-brompropene 2-phenyl-3-chlorpropene 2-naphthyl-3-chlorpropene Vinyl halides Crotyl halides 3-halo-cyclohexene 2-halo1,4-dipheny1 butene-2 3-halo-1,4-pentadiene, etc.

C. Copolymers of non-oxygen and of oxygencontaining polymers e. g. polymers of vinyl chloride with either vinyl acetate, furmaric esters, maleic esters, vinylidene chloride; polymers of ethylene with amylene, styrene, stilbene, vinyl acetate, meta acrylic esters, ethyl itaconate, diethyl citraconate, diethylmaleate, diethylfumerate, maleic anhydride, vinylbutyl ether; chloropene-isobutylene copolymer, butadiene-isobutylene copolymer, reaction product with maleic anhydride, polymethallyl chloride or copolymer thereof with isobutylene, etc.

III. Saturated alkyl mono-carboxylic acids (the required unsaturation linkage being the carboxyl group C. Hydroxy alkyl carboxylic acids (required unsaturatedlinkage being the t group or C=C)-- Dimethyl hydroxy caprylic Dimethyl hydroxy capric Hydroxy phyetoleic Ricinoleic Ricinelaidic 12-hydroxy stearic 9,10-dihydroxy stearic 4-hydroxy palmitic Linusic Sativic Lanoceric Dihydroxy gadoleic Dihydroxy behenic Quince oil acids, etc.

D. Keto acids (required unsaturated linkage being the 0:0 group) Pyronacenic Licanic Propanyl formic 12 keto stearic Butyryl formic Aceto butyric E. Aldehyde alkyl carboxylic acids (required unsaturated linkage being the (7:0 group or the C=C) Aldovaleric Formylacrylic Mucolronic acids, etc.

F. Polycarboxylic alkyl acids (required unsaturated linkage being the C=O group or the @CL- Cycloalkylene, alkylene, arylalkyl malonic Cycloalkylene, alkylene, arylalkyl succinic Cycloalkylene, alkylene, arylalkyl glutaric Cycloalkylene, alkylene, arylalkyl adipic Pimelic Azelic Brassylic Alkylene maleic Furmaric Itaconic Citraconic Mesaconic Glutaconic Tartronic Malic Aspartic Mesoxalic Tricarballytic acids and homologs, e. g.

Aconitic Tartaric 1 Citric acids, etc. The alkyl group of the acid preferably should contain at least 6 carbon atoms.

G. Miscellaneous alkyl acids- Acidic products produced by oxidation of hydrocarbons, e. g.

Olefinic paraffin wax, etc;

Mercapto oleic Mercapto stearic Thio stearic Cetyl alpha amino succinic Amino caprylic Mercapto succinic Cetyl amino succinic Phosphonato fatty acids e. g., phosphonato butyric to stearic acids;

Cyano fatty acids, e. g., cyano butyric to stearic acids 13 keto behenic acids, etc

These phosphonato and cyano acids may also include the polycarboxylic acids e. g. phosphonato alkyl succinic acid, etc.

Either or both of the oxygen atoms in the carboxylic acid radical of A to G may be replaced by sulfur, selenium, and/or tellurium atoms resulting in the following acid radicals: CXOH, COXH, CXXH, wherein X is sulfur, selenium or tellurium. Also these acids may contain substituent groups attached in appropriate position of the acid molecule so as to aid i solubilizing and enhancing their lubricating properties.

IV. Aromatic acids, represented by the general formula wherein Ar is an aromatic nucleus; X and X may be non-polar or polar radicals attached to the aryl nucleus; Z is a carboxylic acid group such as CYYH wherein either or both Y's may be oxygen, sulfur, selenium or tellurium, said acid being attached directly to the aryl nucleus or linked to it through X; m may be zero or an integer of from 1 to 3; n may be zero or one and y may be an integer of 1 or 2. Representative acids are:

Benzoic Phthalic Toluic Xylic Phenyl fatty acids, e. g.

Phenyl acetic to phenyl stearic acids Benzyl acetic to benzyl stearic acid Cinnamic acid Salicylic acid Mendelic acid Phenyl glyoxylic Benzoyl propionic acid Phenyl laevulunic acid Phenyl alkyl succinic acid Benzyl alkyl succinic acid Phenyl alkyl glutaric acid o-Vinyl benzoic acid Phenyl angelic acid Naphthoic acid Naphthylstearic acid Anthranilic acid Phenyl cinnamic acid Methyl cinnamic acid Methoxy cinnamic acid Atropic acid Phenyl crotonic acid Phenyl amino crotonic acid Phenyl acrylic acid Phenyl ricinoleic acid Benzal lactic acid Benzal malonic acid Benzal propionic acid Mercapto (phenyl, tolyl, xylyl, xenyl, naphthyl anthracyl) fatty acids e. g.-

Phenyl mercapto acetic to'phenyl mercapto stearic acid Ethyl mercapto phenyl acetic acid Aryl mercapto benzene-l-carboxylic V. Cyclic acids: Naphthenic acids derived from petroleum hydrocarbons- Cyclohexane carboxylic acid Hexahydrobenzoic acid Tetra hydrotoluic acid Alkylene cyclohexadiene carboxylic acid Abietic acid Alkvl hexahydrophthalic acid Camphane-B-carboxylic acid Camphoric acid and derivatives Cholic acid and derivatives Cholic acid Laurolenic acid Chaulmoogric acid Tetrahydrobenzoic acid Tetrahydrophthalic acid Dihydrophthalic acid Tetrahydroxylic acid Fural acrylic acid Linseed oil fatty acid Oiticica acid Cyclohexylacetic acid Cyclohexylbutyric acid Cyclohexylcaproic acid Cyclohexyl propionic acid Cyclohexyl valeric acid Fencholic acid, etc.

VI. Heterocyclic acids represented by the general formula wherein Q is a five or six-membered heterocyclic ring; R and R may be alkyl, aryl alkaryl, arylalkyl alkoxy; aryloxy radicals; Z is a carboxyl radical, m may be zero or an integer of 1 and 2 and n may be zero or 1 and :11 may be an integer of 1, 2 or 3. Specific heterocyclic acids may include:

Picolinic acid Nicotinic acid Isonicotinic acid Quinolinic acid Cinchomeronic acid Lutidinic acid Berberonic acid Alphaand beta-carbo cinchomeronic acid Quinic acid Cynchomeronic acid;

Pyrole carobxylic acids; Quinoline carboxylic acids; Thiazole carboxylic acids; Thiophene carboxylic acids; etc.

VII. I-G miscellaneous acids such as:

Dithio carbamic acids wherein R is represented by alkyl, aryl, arylalkyl, alkylaryl cyclo radicals and the like. Some specific compounds may be:

Dibutyl mono and dithio carbamic acid Diethyl mono and dithio carbamic acid Dimethyl mono and dithio carbamic acid Diamyl mono and dithio carbamic acid Dioctyl mono and dithio carbamic acid Dipropyl mono and dithio carbamic acid N-ethyl-N-phenyl mono and dithio carbamic acid Octyl-butyl mono and dithio carbamic acid Dicyclohexyl mono and dithio carbamic acid Methyl-octyl mono and dithio carbamic acid Dibenzyl amyl dithiocarbamic acid, etc.

Included under miscellaneous acids of group VII may be the acid anhydrides and acid halides such as:

Acid anhydrides-- Acrylic Butenic Crotonic Pentenic Tiglic Hexenic Teracrylic Hypo li Oleic Linoleic Erucic Hexylacrylic acid Acid anhydride e. g. acrylic acid anhydride Linolenic Brassidic Elaidic Corn oil acid Lard oil acids Soy oil acids Tung oil acids Elacostearic Stearoleic Cocoanut fatty acids Cottonseed oil acids, etc.

Acid halides- Acrylic Butenic Crotonic Pentenic slic Hexenic Teracrylic Hypogalic Oleic Linoleic Erucic Hexylacrylic acid 1 Acid halide, e. g. acrylic acid halide Linolenic Brassidic Elaidic Corn oil acid Lard oil acids Soy oil acids Tung oil acids Elacostearic l0 Stearoleic Cocoanut fatty acids Cottonseed oil acids, etc.

VIII. Organic compounds containing an inoranic acid:

A. Sulfonic acids- Benzene sulfonic acid Toluene sulfonic acid Tri isopropyl naphthalene sulfonic acid Diphenyl sulfonic acid Polyalkyl aromatic sulfonic acid, e. a. poly amy naphthalene sulfonic acid Diwax benzene sulfonic acid Xylene sulfonic acid Benzene disulfonic acid Alkane sulfonic acids, e. g. amyl, octyl, nonyl,

lauryl, dodecyl sulfonic acids Petroleum sulfonic acids derived from various petroleum fractions such as- Gas oil Kerosene Light oil Turbine oil Mineral lubrication oil Heavy oil Petroleum waxes, e. g.

Petrolatum Paraffin wax and mixtures of various hydrocarbon fractions Wax sulfo salicyclic acid Diwax naphthalene sulfonic acids, etc.

IX. Phosphorus-containing acids:

Substituted phosphorus acids containing an organic substituent: the aliphatic, cyclo aliphatic and aromatic acid esters of phosphoric acid, thio phosphoric acids, phosphorus acids and thio phosphorus acids. These are obtained by reacting P0013, P205, PCls, PzSs, P255, P4S7 Br with any of the acids of groups I, A-E, II, .A-C, III, A-G, IV, V, VI, and VII. These inorganic'phosphorus compounds may also be reacted with any of the materials listed under groups X, XI, XII, and XIII, as well as esters which may be formed by reacting the alcohols of groups X and/or XI with the acids of groups III, IV, V, VI and VII.

X. Alcohols and thin alcohols such as RXH wherein X is 0, Se, Te and S and R represents alkylene, cyclo-alkylene, aralkyl radical or derivatives thereof.

A. Aliphatic Vinyl alcohol 2-propyn-1-ol Allgvl alcohol Oleyl alcohol Geraniol Wood fat alcohol Citronellol Olefinic wax Linaliiol Alcohol Farnesol Methallyl alcohol Phytol Allyl alcohol B. Cyclic alcohols Cyclohexanol Alkyl cyclohexanol, e. g.

, Methyl cyclohexer ol Amyl cyclohexenol Cyclobutenol Naphthenic alcohol, etc.

C. Aromatic alcohol Benzyl Phenyl ethyl Dibenzyl Tolyl Phenyl octyl Octadecyl benzyl alcohols, etc.

Alcohols as found in wool fat, sperm 011 Alcohols produced by oxidation of hydrocarbons, e. g.

Paraflin wax Sweat wax Petrolatum and the like XI. Phenolic compounds- (Rr-A1'XH) wherein Ar is an aryl nucleus, X is O, S, Se, Te and R is a substituent non-polar and/or polar group and/or groups.

Phenol Alkylene phenol Dibutyl phenol and its thio phenols Amyl phenol and its thio phenols Tertiary butyl p-Tertiary amyl Octylene p-Iso-octylene Isobutylene Nonylene Cetyl phenols and thio phenols Alkylamino phenol Alkyl amino naphthol Catechol Resorcinol Pyrogallol Allof these compounds may contain substituent groups as listed in column 14 and the like. Substituted products are: hydroquinone, quinone, orcinol, phioro-glucinol, cresols, thymol, saligenin, cinnamyl alcohol, methyl phenyl carbinol, eugenol, cardanols, etc. Also the thio phenolic derivatives of these phenolic compounds may be used as well as various reaction products thereof such as obtained by reacting phenolic compounds with: SC12, S2012, S, S02 and the like to form sulfide derivatives which may be represented broadly by the formula:

XH xH R..-lr-X. r-R- wherein Ar is an aryl nucleus, R is an alkyl, aralalkyl radical and the like, X is S which in turn can be replaced by 0, Se or Te in whole or in part, and u is an integer of from 1 to 4, and Y may be a polar radical such as listed under VII B l2 XII. Aldehydes:

A. Aliphatic (saturated and unsaturated) Acetaldehyde Croton-aldehyde 5 Propionaldehyde Citral, etc.

Butyraldehyde Tiglic aldehyde Caproaldehyde Propiolaldehyde and the like; Valeraldehyde Acrolein Oleyl valeraldehyde B. Aromatic- Benzaldehyde Naphthaldehyde Cinnamaldehyde Tolualdehyde Salicylaldehyde Anisaldehyde l6 XIII. Ketones:

A. Aliphatic (saturated and unsaturated)- Acetone Phorone Butanone Pentanedione Hexanone Mesityl oxide Oleone Diethyl ketone Palmitone B-methyl-heptanone Methyl ethyl ketone Di-isobutyl ketone Methyl propyl ketone Diacetone alcohol Butyrone Ally1acetone,diallylace- Butenone tone Vinylethyl ketone Dioleyl ketone Pentanone and the like 80 B. Aromatic- Acetophenone Benzyl phenyl ketone Propiophenone Benzophenone Dibenzyl ketone and the like C. Cyclic ketones:

Cyclobutenone Cyclopentenone Quinones Cycloheptenone 40 Pure isophorone either or both m and n may be zero or an integer Octyl phenol-formaldehyde Octyl phenol-acetaldehyde Iso octyl phenol-acetaldehyde Iso octyl phenol-crotonaldehyde Octyl phenol-benzaldehyde Octyl phenol-furaldehyde Octyl thio phenol-furaldehyde Octyl thio phenol-formaldehyde Amyl phenol-formaldehyde Amyl phenol-furaldehyde and isophorone bottoms the manufacture of which is fully described hereinbelow Cyclohexenone Carvomenthone Menthone Pulegone Carvone Muscone of from about 300 to about 500 pounds per square inch. The resultant product is subjected to distillation to remove distillable ketones and other constituents and impurities. The product remaining in the still is preferably purified by filtration, solvent treatment, and comprises crude unsaturated cyclic ketones of high molecular weight, preferably referred to as crude isophorone bottoms. The term isophorone bottoms as referred herein is usually a complex mixture of high molecular weight unsaturated cyclic ketones containing at least 12 and preferably more than 18 carbon atoms in the molecule. The product thus formed is not to be confused with straight isophorone which is specifically 3,5,5 trimethyl cyclohexene 2 one 1, which is an unsaturated cyclic ketone containisophorone bottoms produced by condensation of acetone under conditions referred to above includes withinits scope any and all unsaturated cyclic ketones containing at least 12 and preferably more than 18 carbon atoms and having generally the chemical structural configuration of isophorone as well as the chemical structural configuration resulting from its further condensation. I

Crude isophorone bottoms can be fractionated and/or chemically treated and each fraction therefrom can in turn be treated with a peroxide catalized polyhalo organic compound and thereafter treated with H2SNH4HS if desired to produce one of the additives of this invention. Among the various fractions which can be obtained from crude isophorone bottoms are topped, crude isophorone bottoms which contain at least 18 carbon atoms in the molecule and are obtained after removal of distillate from crude isophorone bottoms to a still head temperature of 140 C. at mm. mercury pressure. Another fraction of crude isophorone bottoms can be subjected to hydrolysis with dilute sodium hydroxide and the acetone and isophorone formed removed by distillation. The bottoms can then be filtered and purified and comprise essentially unsaturated cyclic ketones containing at least 12 or more carbon atoms in the molecule and are referred to as crude, hydrolyzed isophorone bottoms. This material can be subjected to distillation to split it into two fractions. The distilled hydrolyzed isophorone fraction has a boiling point of about 140 C. at 10 mm. mercury pressure and consists of a mixture of unsaturated cyclic ketones containing between 15 to 18 carbon atoms in the molecule. The residue is referred to as "topped, crude hydrolyzed isophorone bottoms and is similar to topped crude isophorone bottoms. This residue comprises essentially unsaturated cyclic ketones of at least 15 carbon atoms and higher in the molecule. Crude isophorone bottoms can be also subjected to condensation over solid sodium hydroxide to yield two types of resinous materials. The first resinous fraction or soft resin has a viscosity at 210 F. of about 25-26 centistokes and an average molecular weight of from 320 to 250. The heavier fraction or medium resin has a viscosity at 210 F. of about 25-26 centistokes and an average molecular weight of from 320 to 350. The heavier fraction or medium resin has a viscosity at 210 F. of'about 80 to ,120 centistokes and an average molecular weight of from 370 to- XIV. Natural fats, oils and waxes and their derivatives and miscellaneous compounds:

A. Vegetable and animal oils, fats, and waxes such as Castor oil Cocoanut oil Corn oil Cottonseed oil Horse fat Lard oil Mutton tallow Beef tallow Neats-foot oil 14 Palm oil Peanut oil Rapeseed oll Soya bean oil Sperm oil Whale oil Wool fat Japan wax Olefin waxes Paramn waxes Wax tailings Petrolatum Vegetable and animal phosphatidic materials Montan wax Carnauba wax Beeswax Spermaceti Castor oil distillate Ozokerite Tall oil and the like and fractions and derivatives thereof XV. Esters:

Esters contemplated for use in this invention may be obtained by reacting any of the compounds listed under groups III, A-6. IV. V, VI, and VII, with compounds of groups X and XI. Specific esters are:

Allyl acetate Methyl acrylate Allyl propionate Allyl allyloxylacetic acid Allyl laurate Methyl allyl methallyl Allyl capronate oxyacetic acid Allyl isovalerate Allyl metallyloxyacetate Allyl stearate Glyceryl monoricinoleate Lanyl acrylate Glyceryl monooleate Methyl crotonate XVI. Ethers: The ethers contemplated for use in this in- Allyl succinate vention may be symmetrical, unsymmetrical or mixed ethers of dialkyl ethers, alkyl-aryl ethers, aryl ethers and the like. Specifically it is desirable to use:

B. Cyclic and poly ethers Ethylene oxide Acetal Propylene oxide Dioxan, and the like C. Aromatic ethers Allyloxyphenyl ether Benzyl ether Anisole Cardanoxyethanol Phenetole Allyl-alpha-phenyl vinyl Diphenyl ether Dixenyl Allyl phenyl ether Dinaphthyl ethers and. the like.

Benzyl phenyl ether D. Substituted ethers Alkyloxy ethers of polyhydroxy aromatics such Resorcinal Pyrogallol andthe like.

REAGENT Any of the above compounds and mixtures thereof may be reacted with a polyhalogenated organic compound in the presence 01 a peroxide catalyst. The polyhalogenated organic compounds may include: carbon tetrachloride, chloroiorm, methylene chloride, carbon tetrabromide, bromoform, methylene bromide, iodoform, methylene chlorolodide, hexachloroethane, diand tri-chlorcethane polyhalogenated fatty acids in which the halo radicals are preferably attached in the alpha or beta position to the carboxyl radical. Specific compounds are: dichloroacetic acid, trichloroacetic acid, alpha,alpha-dichloropropionic acid, alpha,alpha, beta,beta-tetrachloropropionic acid, alpha,beta-dichloropropionic acid, alpha,alpha-dichlorobutyric acid, alpha,beta-dichlorobutyric acid, alpha,alpha,beta-trichlorbutyric acid, alpha,beta-dichloroisobutyric acid phenyldichloro acetic acid, dibromo acetic acid, tribromo acetic acid, alpha,alpha-dichloropentanoic acid, alpha,alpha-dibromopentanoic acid, diiodo acetic acid, triiodo acetic acid, beta,betadibromopropionic acid, 'caprylic acid. etc.

CATALYSTS The peroxide catalysts which can be used to carry out the halogenation reaction may include:

The reaction product of this invention, namely, a peroxide catalyzed reaction product between an organic compound having an unsaturated linkage or linkages and a polyhalogenated organic compound can be carried under reflux conditions for a period of time suflicient for the reaction to go to completion. This is evidenced when hydrogen chloride seems to evolve and may require from a few hours to over 72 hours depending upon the reactants taking part in the reaction, the temperature and the like.

Thereaction product of this invention namely a peroxide catalyzed polyhalogenated organic compound can be treated with hydrogen sulfide in the presence of ammonium hydrosulfide to obtain an additive suitable for use as additives in lubricants operating under the most adverse conditions. This reaction can be formed at room or elevated temperatures, preferably in closed vessels. The use of elevated temperatures apparently only speeds up the reaction. However, the cost of fuel and special equipment outweighs this feature, and it has been ordinarily found more advantageous to simply allow the ammonium hydrosulfide-hydrogen sulfide reactions to take place at room temperature in closed vessels for the necessary period of time, e. g. from one week to one month or more, depending upon the organic material being treated. Ii desired alpha,alpha-dichloro- 16 this reaction product may be formed in the presence of a suitable inert solvent.

To more clearly illustrate the present invention, the following examples are presented. It is to be understood, however, that various modifications can be resorted to without departing from the spirit of the invention.

GROUP I Example 1 Reaction product of peroxide catalyzed, topped, crude isophorone bottoms with' carbon tetrachloride-Approximately 1 mole of topped, crude isophorone bottoms; 4 moles of carbon tetrachloride and 0.04 mole of benzoylperoxide were reacted under reflux conditions until the reaction was completed. The excess carbon tetrachloride was removed by distillation. The residue wa a dark, viscous material containing 13.5 to 15.4 per cent chlorine.

Example 11 Reaction product of peroxide catalyzed cracked wax Olefins with carbon tetrachloride. Approximately 1 mole of cracked wax olefins having a molecular weight of about 218, a boiling point range of 220-300 C. and the double bond being present in the terminal position were reacted with carbon tetrachloride in the presence of benzoyl peroxide under conditions as described in Example I. Hydrogen chloride was evolved during'the reaction period. The reaction product formed was a dark red oil which contained approximately 8.7 chlorine and possessed excellent extreme pressure properties.

Example III Example IV Reaction product of peroxide catalyzed topped, crude isophorone bottoms with. chloroform. Approximately one mole of topped, crude isophorone bottoms and chloroform were'reacted in the presence of benzoyl peroxide.

This reaction product in the same manner as described in Example II, except that chloroform was used as the chlorinating agent. The final product was a dark red oil containing about 1.2 to 2.4% chlorine.

Example V Reaction product of peroxide catalyzed cracked wax olefin with. trichloroacetic acid.Approximately 0.5 mol of cracked wax olefins, about 2 moles of trichloroacetic acid and 0.02 mols of ditertiary butyl peroxide was stirred and heated on a steam bath for 24 hours. At the end of the reaction period considerable evolution of hydrogen chloride was noted. The product was dissolved in a non-aromatic solvent as referred to in Example III and excess trichloroacetic acid I? washed out by means of water. The solvent was evaporated leaving behind a dark brown liquid having a chlorine content of approximately 20.8 per cent.

Example VI Reaction product of peroxide catalyzed Ca-C 1a olefin having non-terminal double bonds with tr:- chloroacetic acid.--This reaction product was formed in the manner described in Example V except that an olefin of Ca-Cm having non-terminal double bonds and a molecular 'weight above 185 was utilized. The chlorine content of the final product was approximately 25.8%.

Other peroxide catalyzed polyhalogenated or ganic compounds of this invention are:

1. Reaction product of peroxide catalyzed spray oil and carbon tetrachloride.

2. Reaction product of peroxide catalyzed spray oil and chloroform.

3. Reaction product of peroxide catalyzed hydrogen pressure distillate bottoms and carbon tetrachloride.

4. Reaction product of peroxide catalyzed hydrogen pressure distillate bottoms and chloroform.

5. Reaction product of peroxide catalyzed cracked wax olefins and carbon tetrachloride.

6. Reaction product of peroxide catalyzed cracked wax olefins and chloroform.

'7. Reaction product of peroxide catalyzed cracked wax olefins and dichloroacetic acid.

8. Reaction product of peroxide catalyzed isophorone with carbon tetrachloride.

9. Reaction product of peroxide catalyzed isophorone with chloroform.

10. Reaction product of peroxide catalyzed CeC1s olefin and chloroform.

11. Reaction product of peroxide catalyzed Ce-Cm olefin and carbon tetrachloride.

12. Reaction product of peroxide catalyzed oleic acid and carbon tetrachloride.

13. Reaction product of peroxide catalyzed polymeric ethylene and dichloroacetic acid.

14. Reaction product of peroxide catalyzed allyl alcohol and dichloroacetic acid.

15. Reaction product of peroxide catalyzed cyclohexenone and chloroform.

16. Reaction product of peroxide catalyzed castor oil and chloroform.

17. Reaction product of peroxide catalyzed cinnamyl alcohol and carbon tetrachloride.

18. Reaction product of peroxide catalyzed cinnamic acid and carbon tetrachloride.

19. Reaction product of peroxide catalyzed co- GROUP II Example VII A. Initial reaction product of peroxide catalyzed, topped, crude isophorone bottoms with carbon tetrachloride.--Approximately 1 mole of topped, crude, isophorone bottoms; 4 moles of carbon tetrachloride and 0.04 mole of benzoyl peroxide were reacted under reflux conditions until the reaction was completed with required between 24 to 72 hours. The excess carbon tetrai8 chloride was removed by distillation. The polychlorinated reaction product was a dark viscous material containing approximately 13.5% to 15.4% chlorine.

B. Final reaction product obtained by treating VII-A with H28 in the presence of ammonium hydrosulfide.Approximately grams of the above reaction product was dissolved in 300 cc. of isopropyl alcohol and admixed with 500 cc. of isopropyl alcohol which had been saturated with ammonium hydrosulfide and hydrogen sulfide. Hydrogen sulfide was passed through the resulting mixture until saturated. The reaction vessel was closed and allowed to stand for one week. The reactor was then opened and the isopropyl alcohol solution was filtered and the solvent removed by evaporation. The residue was dissolved in a non-aromatic hydrocarbon having a boiling range of between about 164 F. and 233 F. and washed with water. The solvent and water are removed by suitable means and the resultant product which was a dark brown viscous material contained 2.2% sulfur and 10.4% chlorine. The product was soluble in mineral oil and had excellent extreme pressure properties.

Example VIII A. Initial reaction product of peroxide catalyzed cetene with dichloroacetic acid.-Approximately 0.5 mole of cetene, 2 moles of dichloroacetic acid and 0.02 mole of di-tert-butyl peroxide were admixed and heated on a steam bath for 24 hours. The reaction mixtur was then dissolved in a non-aromatic hydrocarbon having a boiling range of between 164 F. and 233 F. and washed with water to remove excess dichloroacetic acid. After removal of the solvent in vacuo, the product remaining was a dark, viscous liquid containing 14.0% chlorine.

B. Final reaction product obtained by treating 11-11 with His presence of ammonium hydrosulfide.--The reaction product of II-A was dissolved in isopropyl alcohol and admixed with an approximately equal amount of isopropyl alcohol which has been saturated with ammonium hydrosulfide. Hydrogen sulfide was passed through the resulting mixture until saturated. The reaction vessel was opened, the solvent removed and the residue dissolved in a non-aromatic hydrocarbon and water washed. The solvent and water were removed and the residue contained both sulfur and chlorine and exhibited excellent extreme pressure properties when admixed with lubricants.

Other peroxide catalyzed polyhalogenated organic compounds or these which have been further treated with ammonium hydrosulfide-hydrogen sulfide to produce reaction product of this invention are 1. Reaction product of peroxide catalyzed spray oil and carbon tetrachloride treated with hydrogen sulfide-ammonium hydrosulfide.

2. Reaction product of peroxide catalyzed spray oil and chloroform treated with hydrogen sulfideammonium hydrosulfide.

3. Reaction product of peroxide catalyzed hydrocarbon pressure distillate bottoms and carbon tetrachloride treated with hydrogen sulfide-ammonium hydrosulfide.

4. Reaction product of peroxide catalyzed hydrocarbon pressure distillate bottoms and chloroform treated with hydrogen sulfide-ammonium hydrosulfide.

5. Reaction product of peroxide catalyzed cracked wax olefins and carbon tetrachloride 19 treated with hydrogen sulfide' ammonium hydrosulfide.

6. Reaction product of peroxide catalyzed cracked wax olefins and chloroform'treated with hydrogen sulfide-ammonium hydrosulfide.

7. Reaction product of peroxide catalyzed cracked wax olefins and dichloroacetic acid treated with hydrogen sulfide-ammonium hydrosulfide.

8. Reaction product of peroxide catalyzed isophorone with carbon tetrachloride treated with hydrogen sulfide-ammonium hydrosulfide.

9. Reaction product of peroxide catalyzed isophorone with chloroform treated with hydrogen sulfide-ammonium hydrosulfide.

10. Reaction product of peroxide catalyzed wax olefin and chloroform treated with hydrogen sulfide-ammonium hydrosulfide.

11. Reaction product of peroxide catalyzed wax olefin and carbon tetrachloride treated with hydrogen sulfide-ammonium hydrosulfide.

12. Reaction product of peroxide catalyzed oleic acid and carbon tetrachloride treated with hydrogen sulfide-ammonium hydrosulfide.

13. Reaction product of peroxide catalyzed polymer ethylene and dichloroacetic acid treated with hydrogen sulfide-ammonium hydrosulfide.

14. Reaction product of peroxide catalyzed allyl alcohol and dichloroacetic acid treated with hydrogen sulfide-ammonium hydrosulfide.

15. Reaction product of peroxide catalyzed cyclohexenone and chloroform treated with hydrogen sulfide-ammonium hydrosulfide.

16. Reaction product of peroxide catalyzed castor oil and chloroform treated with hydrogen sulfide-ammonium hydrosulfide.

17. Reaction product of peroxide catalyzed cinnamyl alcohol and chloroform treated with hydrogen sulfide-ammonium hydrosulfide.

18. Reaction product of peroxide catalyzed cinnamyl acid and chloroform treated with hydrogen sulfide-ammonium hydrosulfide.

19. Reaction product of peroxide catalyzed copolymer of butadiene-isobutylene and dichloroacetic acid treated with hydrogen sulfide-ammonium hydrosulfide.

20. Reaction product of peroxide catalyzed copolymers of ethylene vinyl butyl ether and carbon tetrachloride treated with hydrogen sulfide-ammonium hydrosulfide.

Reaction product of this invention may be neutralized with a suitable metal or organic base to form salts. Alkali and alkaline earth metals, heavy metals, amines and quaternary ammonium compounds may be used. Preferred are: Na, Li, K, Ca, Ba, Sr, Mg, zn, Al, Cr, Co, Ni primary and secondary amines and the like.

To illustrate the pronounced improvement obtained in lubricating compositions by the addition of reaction products of this invention the balls arranged in pyramid formation. The top ball is rotated by spindles against the three bot-v tom balls which are clamped in a stationary ball holder. The balls are immersed in the composition to be tested. Tests were run under conditions indicated in the table and compared with other outstanding extrem pressure agents.

' agents and the like.

FOUR-BALL E. P. LUBRICANT TESTER ON ADDIIIVES IN SAE 90 OIL [Fixed conditions: One-minute tests at 1500 R. p. m.]

Scar Diametcr, in mm. at 300 Kg. load Amt, Per Cent wt.

Seizure Welding Load, Load, in Kg. in Kg.

Additive 1 None 50 In addition to the above properties the addition of reaction products of this invention to mineral lubricating oils inhibits lacquer formation in engines operating under the most adverse conditions. Also reaction product of this invention can be used as valuable constituents of heavy duty oils, motor oils, diesel oils, aviation oils, turbine oil, synthetic oils and the like because of their anti-corrosion, anti-oxidation, and antiwear properties. Besides their utility as lubricating oil additives, reaction products of this invention are useful as anti-oxidants for natural and synthetic rubber and other organic materials which are subject to oxidation deterioration. The amount of additive used can be varied over wide limits but generally it is not necessary to use more than 5% by weight of the reaction product although amounts of as high as 10% can be used but preferably only between' about 0.1 to 2.0% by weight is added to base lubricants.

Because of its synergistic effect the reaction product of this invention can be combined with other additives in lubricants. such as, blooming agents, pour point depressants or viscosity improvers, extreme pressure agents, anti-foaming Among the specific additives which can be used are oil-soluble detergents which include oil-soluble salts of various bases with detergent forming acids. Such bases include metal as well as organic bases. Metallic bases include those of the alkali metals, Cu, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb, Cr, Mn, Fe, Ni, Co, etc. Organic bases include various nitrogen bases as primary, secondary. tertiary and quaternary amines.

Examples of detergent forming acids are the various fatty acids of, say, 10 to 30 carbon atoms. wool fat acids, paraflin wax acids (produced by oxidation of paraffin wax) chlorinated fatty acids, rosen acids, aromatic carboxylic acids including fatty acids, aromatic hydroxy fatty acids. paraf- 21 fin Wax benzoic acids, various alkyl salicylic acids, phthalic acid monoesters, aromatic keto acids, aromatic ether acids, diphenols as di-(alkylphenol) sulfides and disulfides, methylene bis alkylphenols; sulfonic acids such as may be produced by treatment'of alkyl aryl hydrocarbons or high boiling petroleum oils with sulfuric acid;

1 sulfuric acid monoesters; phosphoric, arsonic and cephlin, certain fatty oils as rapeseed oils, voltolized fatty or mineral oils and the like.

An excellent metallic detergent for the present purpose is the calcium salt of oil-soluble petroleum sulfonic acids. This may be present advantageously in the amount of about 0.025% to 0.2% sulfate ash. Also alkaline metal salts of alkyl phenol-aldehyde condensation reaction products are excellent detergents.

Anti-oxidants comprise several types, for example, alkyl phenols such as 2,4,6 trimethyl phenol, penta methyl-phenol, 2,4, dimethyl-G-tertiary-butyl phenol, 2,4-dimethyl-6-octyl phenol, 2,6-di-tertiary-butyl-4-methyl phenol, 2,4,6 tritertiary-butyl phenol and the like; amino phenols as benzyl amino phenols; amines such as dibutyl-phenylene diamine, diphenyl amine, phenyl beta naphthylamine, phenyl alphanaphthylamine, dinaphthyl amine.

Corrosion inhibitors or anti-rusting compounds may also be present, such as dicarboxylic acids of 16 and more carbon atoms; alkali metal and alkaline earth salts of sulfonic acids and fatty acids; organic compounds containing an acidic radical in close proximity to a nitrile, nitro or nitroso group (e. g. alpha cyano stearic acid).

Extreme pressure agents which may be used comprise: esters or phosphorus acids such as triaryl, alkyl hydroxy aryl, or aralkyl phosphates, thiophosphates or phosphites and the like; neutral aromatic sulfur compounds or relatively high sulfide, corresponding diand tri-sulfides, and

the like; sulfurized fatty oils or esters of fatty acids and monohydric alcohols, e. g. sperm oil, jojoba oil, etc. in which the sulfur is strongly bonded; sulfurized long chain olefins such as may be obtained by dehydrogenation or cracking of wax; sulfurized phosphorized fatty oils or acids, phosphorus acid esters having sulfurized organic radicals, such as esters of phosphoric or phosphorus acids with sulfurized hydroxy fatty acids; chlorinated hydrocarbons, such as chlorinated parafiin, aromatic hydrocarbons, terpenes, mineral lubricating oil, etc.; or chlorinated esters of fatty acids containing the chlorine in position other than alpha position.

Additional ingredients may comprise oil-soluble urea or thiourea derivatives, e. g. urethanes, allophanates, carbazides, carbazones, etc.; polyisobutylene polymers, unsaturated polymerized esters of fatty acids and monohydric alcohols and other high molecular weight oil-soluble compounds. Depending upon the additive used and conditions under which it is used, the amount of additive used may vary from 0.01 to 2% or higher. However, substantial improvement is obtained by using amounts ranging from 0.1 to 0.5% in combination with phosphorous sulfide-unsaturated cyclic ketone reaction products of this invention.

It is to be understood that while the features of the invention have been described and illustrated in connection with certain specific examples, the invention, however, is not to be limited thereto or otherwise restricted, except by the prior art and the scope of the appended claims.

I claim as my invention:

1. A lubricant comprising a major amount of a mineral oil and a minor amount, sufiicient to impart extreme pressure properties to said mineral oil, of a reaction product obtained by reacting an unsaturated organic compound selected from the group consisting of unsaturated cyclic ketone fractions containing at least 12 carbon atoms and monooleflnic aliphatic hydrocarbons containing at least 8 carbon atoms, with a polychlorinated saturated organic compound selected from the group consisting of polychlorinated hydrocarbons of from 1 to 2 carbon atoms and polychlorinated fatty acids of not more than 6 carbon atoms having at least 2 chlorine atoms which are separated from the carboxyl group of said acids by not more than 2 carbon atoms, in the mole ratio of from 1:1 to 1:4 respectively, in the presence of a peroxide catalyst under reflux conditions, and further treating said reaction product with hydrogen sulfide-ammonium hydrosulfide at above room temperature until saturated.

2. A lubricant comprising a major amount of a mineral oil and a minor amount of between about 0.1% and about 10.0% of a reaction product obtained by reacting an unsaturated cyclic ketone fraction containing at least 12 carbon atoms with carbon tetrachloride in the mole ratio of 1:1 to 1:4, respectively, in the presence of benzoyl peroxide under refiux conditions and further treating said reaction product with hydrogen sulfideammonium hydrosulfide at above room temperature until saturated.

3. A lubricant comprising a major amount of a mineral lubricating oil and a minor amount of between about 0.1% and about 10.0% of a reaction product obtained by reacting an isophorone bottoms fraction with carbon tetrachloride in the mole ratio of 1:1 to 1:4, respectively, in the presence of benzoyl peroxide under reflux conditions and further treating said reaction product with hydrogen sulfide-ammonium hydrosulfide at above room temperature until saturated.

4. A lubricant comprising a major amount of a mineral oil and a minor amount, sufficient to impart extreme pressure properties to said mineral oil, of a reaction product obtained by reacting an unsaturated organic compound selected from the group consisting of unsaturated cyclic ketone fractions containing at least 12 carbon atoms and monoolefinic aliphatic hydrocarbons containing at least 8 carbon atoms, with a polychlorinated saturated organic compound selected from the group consisting of polychlorinated hydrocarbons of from 1 to 2 carbon atoms and polychlorinated fatty acids of not more than 6 carbon atoms having at least 2 chlorine atoms which are separated from the carboxyl group of said acids by not more than 2 carbon atoms, in the mole ratio of from 1:1 to 1:4 respectively, in the presence of a peroxide catalyst under reflux conditions.

bottoms fraction.

6. The composition of claim 4 wherein the unsaturated organic compound is a cracked wax olefin.

7. The composition of claim 4 wherein the unsaturated organic compound is hexadecene-l.

8. The composition of claim 4 wherein the polychlorinated saturated organic compound is carbon tetrachloride.

9. The composition of claim 4 wherein the polychlorinated saturated organic compound is dichloroacetic acid.

10. A lubricant comprising a major amount of a mineral oil and a minor amount of between about 0.1% and about 10.0% of a reaction product'obtalned by reacting an unsaturated cyclic ketone fraction containing at least 12 carbon atoms with carbon tetrachloride in the mole ratio of 1:1 to 1:4, respectively, in the: presence of benz'oyi peroxide under reflux conditions.

11. A lubricant comprising a. major amount of a mineral lubricating oil and a minor amount of between about 0.1% and about 10.0% or a reaction product obtained by reacting an isophorone bottoms fraction with carbon tetrachloride in.the mole ratio of 1:1 to 1:4, respectively, in the presence of benzoyl peroxide under reflux conditions.

12. A lubricant comprising a major amount of a mineral lubricating oil and a minor amount of between about 0.1 and about 10% o! a reaction product obtained by reacting hexadecene-l with dichloroacetic acid in the mole ratio of 0.5 to 2 respectively, in the presence of ditertiary butyl peroxide under reflux conditions.

DAVID E. ADELSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. A LUBRICANT COMPRISING A MAJOR AMOUNT OF A MINERAL OIL AND A MINOR AMOUNT, SUFFICIENT TO IMPART EXTREME PRESSURE PROPERTIES TO SAID MINERAL OIL, OF A REACTION PRODUCT OBTAINED BY REACTING AN UNSATURATED ORGANIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF UNSATURATED CYCLIC KETONE FRACTIONS CONTAINING AT LEAST 12 CARBON ATOMS AND MONOOLEFINIC ALIPHATIC HYDROCARBONS CONTAINING AT LEAST 8 CARBON ATOMS, WITH A POLYCHLORINATED SATURATED ORGANIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF POLYCHLORINATED HYDROCARBONS OF FROM 1 TO 2 CARBON ATOMS AND POLYCHLORINATED FATTY ACIDS OF NOT MORE THAN 6 CARBON ATOMS HAVING AT LEAST 2 CHLORINE ATOMS WHICH ARE SEPARATED FROM THE CARBOXYL GROUP O F SAID ACIDS BY NOT MORE THAN 2 CARBON ATOMS, IN THE MOLE RATIO OF FROM 1:1 TO 1:4 RESPECTIVELY, IN THE PRESENCE OF A PEROXIDE CATALYST UNDER REFLUX CONDITIONS, AND FURTHER TREATING SAID REACTION PRODUCT WITH HYDROGEN SULFIDE-AMMONIUM HYDROSULFIDE AT ABOVE ROOM TEMPERATURE UNTIL SATURATED. 